Thermodynamics - Calorific Capacity

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SUMMARY

The discussion focuses on deriving the relationship between heat capacities at constant pressure (CP) and constant volume (CV) in thermodynamics. The total differential of entropy (dS) is expressed in terms of temperature (T) and volume (V) derivatives, leading to the equation CP - CV = T(dS/dT). The user initially misapplies the partial derivatives, particularly in the context of constant pressure assumptions, which leads to confusion in their calculations. Clarification is provided regarding the correct interpretation of the partial derivatives involved.

PREREQUISITES
  • Understanding of thermodynamic concepts such as entropy and heat capacity.
  • Familiarity with partial derivatives and their applications in thermodynamics.
  • Knowledge of the first law of thermodynamics and state functions.
  • Basic proficiency in calculus, particularly in differentiating functions of multiple variables.
NEXT STEPS
  • Study the derivation of the Maxwell relations in thermodynamics.
  • Learn about the implications of the first law of thermodynamics on heat capacity.
  • Explore the relationship between CP and CV in different thermodynamic processes.
  • Investigate the role of pressure in thermodynamic equations and its impact on state functions.
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Students of thermodynamics, physicists, and engineers seeking to deepen their understanding of heat capacities and their mathematical relationships in thermodynamic systems.

Jalo
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Homework Statement



Consider a system with a constant number of particles.
Write the total differential dS in terms of the derivarives [itex]\frac{∂S}{∂T}[/itex] and [itex]\frac{∂S}{∂V}[/itex]. Introduce CV (calorific capacity at constant volume).
Next write the total differential of the volume dV in terms of the parcial derivatives [itex]\frac{∂V}{∂T}[/itex] and [itex]\frac{∂V}{∂P}[/itex]. Assume that the pressure is constant. Show that the result comes in the form of:

CP-CV= Expression

Homework Equations



CP=T[itex]\frac{∂S}{∂T}[/itex] , P and N Constant
CV=T[itex]\frac{∂S}{∂T}[/itex] , V and N Constant


The Attempt at a Solution



First I wrote the differential of the entropy as asked:

dS = [itex]\frac{∂S}{∂T}[/itex]dT + [itex]\frac{∂S}{∂V}[/itex]dV

I know that [itex]\frac{∂S}{∂V}[/itex] = CV/T. Substituting I get:

dS = CV/T dT + [itex]\frac{∂S}{∂V}[/itex]dV

Next I found the differential of the volume:

dV = [itex]\frac{∂V}{∂T}[/itex]dT + [itex]\frac{∂V}{∂P}[/itex]dP

Since the pressure is constant it reduces to the form

dV = [itex]\frac{∂V}{∂T}[/itex]dT

Substituting in our dS expression we get:

dS = CV/T dT + [itex]\frac{∂S}{∂V}[/itex][itex]\frac{∂V}{∂T}[/itex]dT =
= CV/T dT + [itex]\frac{∂S}{∂T}[/itex]dT =
= CV/T dT + CP/T dT ⇔
⇔ T[itex]\frac{dS}{dT}[/itex] = CV + CP

I'm making some mistake. If anyone could point me in the right direction I'd appreciate.

Thanks!
 
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I think your problem is a confusion over the meanings of different partial derivatives. Your use of ##\frac{∂S}{∂V}## refers to changing volume, keeping temperature constant.
That's inconsistent with later equating ##\frac{∂S}{∂V}\frac{∂V}{∂T} = \frac{∂S}{∂T}##, which, to be valid, assumes pressure constant in all terms.
 

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